1 amino-4-(4,5 dialkyl-3-sulfamoyl-phenylamino) anthraquinone-2-sulfonic acids

ABSTRACT

A process for producing 1-amino-4-(4&#39;&#39;,5&#39;&#39;-di-lower alkyl-3sulphamoyl-phenyl)-amino anthraquinones is described which affords very high yields of these novel dyestuffs free from byproducts and involves the reaction of a 1-amino-4halogenoanthraquinone with a 1-amino-4,5-dialkyl-3-sulphamoylbenzene. The novel anthraquinones which preferably bear a sulphonic acid group in 2-position at the anthraquinone nucleus are practically free from isomers having a sulphamoyl group in 2or 6-position at the 4,5-dialkylphenylamino moiety, and dye natural and synthetic polyamide fibres in level vivid, pure blue shades of good fastness properties, especially fastness to light; the brilliance of the shade does not suffer even when observed under artificial light.

United States Patent Hindermann et al. Jan. 7, 1975 1 AMINO-4-(4,5 1,987,538 1/1935 Peter 260/374 DIALKYL-3-SULFAMOYL-PHENYLAMINO) 395 91 fg f:

, 1n ermann ANTHRAQUINONE'Z'SULFONIC ACIDS 3,430,771 11/1947 Kern 260/2471 A [75] Inventors: Peter Hindermann, Bottmingen;

m" Meindl, Riehen, both of Primary Examiner-James A. Ratten Swltzerland Assistant Examiner-Michael Shippen [73] Assignee: Ciba Geigy AG, Basel Switzerland Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [22] Filed. Sept. 7, 1973 ABSTRACT [21] Appl. No.: 395,108 A process for producing l-amino-4-(4,5-di-lower al- Related U.S. Application Data kyl-3-sulphamoyl-phenyl)-amino anthraquinones is de- [62] Division Of Ser. NO. 715,990, March 25, 1968, Pat. scribed which affords y high yifilds of these novel Nu 7 dyestuffs free from by-products and involves the reaction of a l-amino-4-halogenoanthraquinone with a l- 30 Foreign Application priority Data amino-4,5-dialkyl-3-sulphamoyl-benzene. The novel Apr. 5 1967 Switzerland 4892/67 anthraquinones which Preferably bear Sulphomc acid group in 2-position at the anthraquinone nucleus 52] us. c1 260/2471 A, 260/247.1 R, are Practically free from f? having sulphamoy' 260/293.62,260/293.73, 260 543 R gFOUP or 6'POSItIO" the [51 I Int. Cl. C09b 1/34, C09b 1/36 dmnfylphenylmmo w natural and 581 Field Of Search 260/247.l A 293.62 POYamde fibres level Pure blue Shades of good fastness properties, especially fastness to light; [56] References Cited the brilliance of theshade does not suffer even when UNITED STATES PATENTS observed under art1f1c1al l1ght. 1,875,191 8/1932 Koch 260/374 2 Claims, N9 Drawings 1 AMINO-4-(4,5 DIALKYL-3-SULFAMOYL-PHENYLAMINO) ANTHRAQUINONE-2-SULFONIC ACIDS This is a, (X) division, of application Ser. No. 715,990, filed Mar. 25, 1968, now U.S. Pat. No. 3,778,453.

The present invention relates to a novel process for the production of new acid anthraquinone dyestuffs, to these dyestuffs, themselves, to processes for the dyeing and printing of organic materials, particularly of natural and synthetic polyamide fibre materials therewith, as well as to such materials dyed or printed with the aid of the new dyestuffs,

The condensation of l-amino-4-halogenoanthraquinone-2-sulphonic acid with aminobenzene sulphonic acid-N-mono-hydroxyalkylamides has been disclosed in German Pat. No. 709,689. The reaction is performed in a conventional manner in an aqueous medium in the presence of copper or copper salts and of acid binding agents, at temperatures of about 50 to 100C. If the condensation is performed at temperatures of 80 to 100C, then a large amount of byproducts is formed in addition to the desired anthraquinone dyestuff. It is known that the proportion of these undesirableby-products can be reduced by limiting the 25 amount of acid binding agents or by working at lower temperatures or by a combination of both of these measures. However, at temperatures below 80C, the condensation of, for instance, l-amino-4-bromoanthraquinone-2-sulphonic acid with l-amino-4- methylbenzene-3-sulphonic acid ethanolamide, only proceeds very slowly and, when operating at a reaction temperature of 70 to 75C and for a reasonable reaction time of 2 to 5 hours, only small amounts of the desired anthraquinone dyestuff are formed.

It has now been found that, surprisingly, the condensation of 1-amino-4-halogeno-anthraquinone-2- sulphonic acid with novel lower alkyl-substituted 1- amino-lower alkylbenzene-3-sulphonic acid amides which are distinguished from the above-mentioned l-aminobenzene-Ii-sulphonic acid amides by bearing two lower alkyl groups, one in 4- and the other in 5- position at the benzene nucleus proceeds practically quantitatively under the aforesaid conditions. It is, indeed, most unexpected that such a favourable result is obtained when using the new l-amino-4,5-di-lower alkylbenzene-Ii-sulphonic acid amides as starting materials in lieu of the known l-amino-4-methylbenzene-3- sulphonic acid amides in the condensation with 1- amino-4halogeno-anthraquinone-Z-sulphonic acid.

Thus, the present invention provides a process for the production of new, valuable acid anthraquinone dyestuffs of the general formula I NHz wherein M* represents one equivalent weight of a colourless cation, X represents hydrogen or a monovalent substituent inert under the reaction conditions defined below, Z, and Z, independently of each other represent identical or different lower alkyl groups, R, represents a lower, unsubstituted or substituted alkyl group, and R represents hydrogen or a lower, unsubstituted or substituted alkyl group or R and R together with the nitrogen atom to which they are linked can alsoform the radical of a 5- or 6-membered heterocyclic ring, optionally, with the inclusion of a further hetero atom as ring member in the latter, by reacting an anthraquinone compound of the general formula ll wherein X and M have the meanings given in formula I and Y represents a halogen atom, particularly bromine, with a novel amine of the general formula III HQN- Zz t s om wherein R,, R Z, and 2, have the meanings given in formula I, the reaction being performed at a temperature in the range of from to 100C in an aqueous medium having a pH of at least 5, preferably-a pH of at least 7, and in the presence of an acid-binding agent and a copper catalyst, to form an anthraquinone dye- 5 stuff of the general formula I.

As monovalent substituent, X in the foregoing formulae represents, e.g., halogen such aschlorine or bromine, lower alkyl groups such as the methyl or ethyl group, also the sulphonic acid group. Preferably, however, X represents hydrogen.

Lower alkyl groups in the position of Z, and Z, are, e.g., the methyl, ethyl, nor isopropyl group. Preferably each of Z, and 2,, represents the methyl group.

As lower, unsubstituted alkyl groups, R, and R represent, e.g., the methyl, ethyl or isopropyl group; as lower substituted alkyl groups, advantageously they represent an alkyl group substituted by hydroxyl such as the B-hydroxyethyl or 'y-hydroxypropyl group; however, they can also represent an alkyl group substituted by a lower alkoxy, hydroxy-lower alkoxy or lower alkoxy-lower alkoxy group, e.g., the ymethoxypropyl, B-hydroxy-ethoxyethyl or B-methoxyethoxyethyl group. If R, and R, together with the nitrogen atom to which they are linked, form a o-membered heterocyclic ring, optionally with the inclusion of another hetero atom in the latter, then this is, e.g., the piperidide or morpholide group. Preferably, however, R, is a hydrox- (III) yalkyl group, particularly the 'y-hydroxyethyl group,

and R is hydrogen.

Chlorine and, particularly, bromine are suitable as halogen atoms in the position of Y.

The starting materials of formula II are known. The following are given as examples of particularly suitable starting materials: l-amino-4-bromoanthraquinone-2- sulphonic acid, l-amino-4-bromoanthraquinone-2,5-, -2,6- and -2,8-disulphonic acid, l-amino-4-bromo-7- chloroanthraquinone-2-sulphonic acid, l-amino-4,6- dichloroor l-amino-4,6-dibromo-anthraquinone-2- sulphonic acid.

The novel l-amino-4,5-di-lower alkylbenzene-3- sulphonic acid amides of formula III which are suitable as starting materials in the process of the invention are obtained, for example, by nitrating a l,2-di-lower alkylbenzene, isolating the l-nitro-4,5-di-lower alkylbenzene in a conventional manner from the mixture of isomers formed, converting it with chlorosulphonic acid into the corresponding 1-nitro-4,5-di-lower alkylbenZene-3-sulphonic acid chloride and then reacting the latter with an amine of formule IV wherein R and R have the meanings given in formula I, to form the corresponding l-nitro-4,5-di-lower alkyl- 3-sulphonic acid amide and thereafter reducing the nitro group to the amino group.

The following are mentioned as particularly suitable l-amino-4,5-di-lower alkylbenzene-3-sulphonic acid amides falling under formula Ill: l-amino-4,5- dimethylbenzene-B-sulphonic acid ethanolamide, lamino-4,5-dimethylbenzene-3-sulphonic acid-N,N-di- (B-hydroxyethyD-amide, l-amino-4,5- dimethylbenzene-3-sulphonic acid-N-methyl-N-B- hydroxyethylamide, 1-amino-4,5-dimethylbenzene-3- sulphonic acid-N-y-methoxypropylamide, l-amino- 4,5-dimethylbenzene-3-sulphonic acid-N-(methoxyethoxy-ethylamide), l-amino-4,5-dimethylbenzene-3- sulphonic acid-N,N-dimethylamide, l-amino-4,5- dimethylbenzene-3-sulphonic acid-N-methylamide, 1- amino-4,5-dimethylbenzene-3-sulphonic acid-N-B- hydroxyethyl-N-ethylamide, l-amino-4,5 dimethylbenzene-3-sulphonic acid morpholide, 1- amino-4,S-diethylbenzene-3-sulphonic acid morpholide and I-amino-4,5-di-isopropylbenzene-3-sulphonic acid ethanolamide.

The starting compounds of formulae II and III are advantageously used in a molar ratio in the range of from about 1:1.05 to 1:1.5, i.e., an excess of the compound of formula III is recommended.

The condensation of an anthraquinone compound of formula II with an amine of formula III is advantageously performed at temperatures between 60 to 100C, more preferably at 70 to 85C, and optimally at 70 to 75C, in water or aqueous-organic solution and in the presence of a copper catalyst and an acid binding agent. It proceeds smoothly, produces a very high yield without formation of undesirable byproducts and is practically complete after 2 to 4 hours reaction time.

Particularly suitable copper catalysts are, e.g., metallic copper or copper salts, preferably cuprous salts such as cuprous chloride, bromide, iodide, acetate, sulphate, or cuprous oxide. Preferably, metallic copper powder is used. Also mixtures e.g., of cuprous chloride and metallic copper powder have proved to be very advantav geous. The catalysts need only be added in small amounts.

The acid anthraquinone dyestuffs of formula I are preferably isolated as alkali metal salts, in particular as sodium salts.

The new acid anthraquinone dyestuffs are suitable for the dyeing and printing of organic materials, particularly of natural and synthetic polyamide fibre material, principally wool but also nylon or polyurethane fibres. At higher temperatures, the new dyestuffs draw evenly from a weakly acid to acid bath and have good levelling and migration properties. The dyeings so obtained are distinguished by vivid, pure blue shades which have very good fastness properties, particularly they have excellent fastness to light. Compared with the anthraquinone dyestuffs disclosed in German Pat. No. 709,689 which contain a single methyl group in 4- position at the phenylamino moiety, they are distinguished, in addition, by their better constancy of colour in artificial light and also, without exception, by somewhat better wet fastness properties.

It is well known that dyed fabrics especially of poly amide fibres appear in different shades depending on whether they are viewed in broad daylight, and especially in sun-light, on the one hand, or in weaker light, especially in artificial, e.g., electric light, on the other hand. The shade which these fabrics show under the latter type of illumination is also referred to as evening shade, while the shade in which the fabrics appear in daylight, may be referred to as normal shade". It can thus happen that a fabric having a brilliant blue normal shade has a dull, red-tinged blue evening shade. It is therefore desirable that the difference between normal shade and evening shade be as small as possible. Hence, constancy of shade under different types of illumination is an important advantage.

The following Examples illustrate the invention. The temperatures are given in degrees Centigrade.

EXAMPLE 1 50.6 g of the sodium salt of bromoanthraquinone-Z,6-disulphonic acid, 29.5 g of 1-amino-4 ,5-dimethylbenzene-3-sulphonic acid ethanolamide and 20 g of sodium bicarbonate are added to 300 ml of water. The mixture is heated to a temperature of to and, while stirring well at this temperature, 0.5 g of copper powder are added in small batches within 30 minutes. To complete the formation of the dyestuff, the reaction mixture is stirred for another 3 hours at 80 to 85, whereupon the dyestuff formed is precipitated by adding sodium chloride to the reaction solution. The precipitate is separated by filtration, washed with aqueous 15 percent sodium chloride solution and dried. The sodium salt of the dyestuff corresponds to the formula l-amino-4- S OSNd.

| S OzNH-CHr-CHz-OH NaOaS and is a dark blue powder which dissolves in concentrated sulphuric acid with a cloudy green-blue shade and in water with a pure green-blue shade. The dyestuff dyes wool and synthetic polyamide fibres from a dyebath acidified with acetic acid, formic acid or sulphuric acid in level greenish blue shades which have very good fastness to light.

The l-amino-4,5-dimethylbenzene-3-sulphonic acid ethanolamide used (M.P. l23.5- 124) is produced as follows: l-nitro-4,5-dimethylbenzene is dissolved in chlorosulphonic acid and the solution is stirred for 8 hours at 100 to 110. It is then cooled to room temperature and, while stirring vigorously, it is poured into a mixture of ice and water. The precipitated l-nitro-4,5- dimethylbenzene-3-sulphonic acid chloride is filtered off and washed with water until the washing water is neutral. The crude sulphochloride can be purified by crystallisation from petroleum ether and then melts at 100 to 101. The recrystallised sulphochloride is then reacted in aqueous suspension with ethanolamine at 50 to 60, the pH being kept constant at 7 to 7.5, to form the corresponding l-nitro-4,S-dimethylbenzene- 3-sulphonic acid ethanolamide which precipitates in very high yield and great purity from the reaction mixture. Recrystallised from alcohol, l-ni tro-4,5- dimethylbenzene-3-sulphonic acid ethanolamide melts at 1l4.5 to ll5.5. This nitro compound is then reduced to the corresponding amine according to Bechamps. The yield thereof is quantitative for all practical purposes.

When repeating Example 1 as a comparison, with 29.5 g of 1amino-2,6-dimethylbenzene-3-sulphonic acid ethanolamide in lieu of l-amino-4,5- dimethylbenzene-3-siilphonic acid ethanolamide, thin layer chromatography of the reaction mixture after the latter has been stirred for 60 minutes following the addition of copper powder shows no formation at all of blue anthraquinone dyestuff, while most of the blue dyestuff has been formed when using the lastmentioned amine as described in Example I.

By repeating the above Example, but using instead of 50.6 g of the sodium salt of l-amino-4-bromoanthraquinone-Z,6-disulphonic acid an equivalent amount of the corresponding 4-chloro derivative and otherwise following the procedure given in the Example, the same blue dyestuff is obtained.

8 EXAMPLE 2 a. 40.4 g of the sodium salt of l-amino-4- bromoanthraquinone 2-sulphonic acid are slurried in 300 ml of water. 37.44 g of ,l-amino-4,5- dimethylbenzene-3-sulphonic acid-N,N-di-(B- hydroxyethyD-umide (as viscous oil) and g of sodium bicarbonate are added to this suspension and the reaction mixture is heated to 75 to 80. While stirring vigorously at this temperature, a homogeneous mixture consisting of 0.25 g of copper powder and 0.25 g of copper-(l) chloride is added within 45 minutes. To complete the formation of the dyestuff, the whole is stirred for another 4 hours at to the reaction mixture is then cooled to room temperature, acidified with dilute hydrochloric acid until a dropped sample turns congo red paper blue and then the precipitated dye acid of the formula is filtered off and the residue is washed with dilute hydrochloric acid. The dye acid is then slurried in 300 ml of water and is dissolved at a neutral reaction by the dropwise addition of dilute aqueous sodium hydroxide solution. It is precipitated in the form of the sodium salt by adding sodium chloride to the solution, filtered off, washed and dried. The sodium salt so obtained is a dark blue powder which dissolves in concentrated sulphuric acid with a greenish blue and in water with a pure blue colour. The dyestuff dyes wool and synthetic polyamide fibres from an acetic acid or sulphuric acid bath in level, pure blue shades which have excellent fastness to light.

b. By repeating the above Example, but using instead of 37.44 g of l-amino-4,5-dimethylbenzene-3- sulphonic acid-N,N-di-(B-hydroxyethyU-amide, 33.54 g of l-amino-4,5-dimethylbenzene-3-sulphonic acid-N- methyl-N-B-hydroxyethyl-amide (MP. 99-100) and otherwise following the procedure given in the Example, a blue dyestuff having similar properties as that of Example 2 (a) is obtained.

EXAMPLE 3 S OaNa O 1IN CH3 is precipitated from the solution in the form of the so dium salt by the addition of sodium chloride and is filtered off and dried. It is a dark blue powder which dissolves in concentrated sulphuric acid with a greenish blue and in water with a pure blue shade. The dyestuff dyes wool and synthetic polyamide fabric from an aqueous dyebath acidified with acetic acid or sulphuric acid in level, non-skittery, blue shades which have very good fastness to light.

b. A dyestuff similar properties is obtained by using,

instead of the 38.08 g of l-amino-4,5- dimethylbenzene-3-sulphonic acid-N-ymethoxypropylamide, 42.28 g of l-amino-4,5-

dimethylbenzene-3-sulphonic acid-N-(B-methoxyethoxy-ethylamide) and otherwise following the procedure given in Example 3.

EXAMPLE 4 a. 40.4 g of the sodium salt of l-amino-4- bromoanthraquirione-Z-sulphonic acid are slurried at 60 to 65 in 300 ml of water. 26.84 g of 1-amino-4,5- dimethylbenzene-3-sulphonic acid ethanolamide are added and the temperature of the mixture is raised to 70 to 75. At this temperature, 20 g of sodium bicarbonate are added and, while stirring well, 0.5 g of copper-(l) chloride are added within minutes. On continuing stirring at 70 to 75, the blue dyestuff formed gradually precipitates in the form of the shimmering, pure sodium salt. After stirring for 3 hours the dyestuff of the formula is precipitated at 60 in the form of the sodium salt by the addition of the sodium chloride. It is filtered, washed with 5 percent aqueous sodium chloride solution and dried. It is a dark blue dyestuff powder which dissolves in concentrated sulphuric acid with a greenish blue and in water with a clear blue colour. The yield is quantitative for all practical purposes. The dyestuff dyes wool and synthetic polyamide fibres as well as mixed fabrics made of the two fibres mentioned from an aqueous dyebath acidified with acetic acid or sulphuric acid in pure blue shades. The dyeings have very good fastness to light and good colour in artificial light.

b. By using instead of 26.84 g of 1-amino-4,5- dimethylbenzene-3-sulphonic acid ethanolamide, 31.68 g of 1-amino-4,5-dimethylbenzene-3-sulphonic acid-N-hydroxyethoxy-ethylamide and otherwise following the procedure given in Example 4, a blue dyestuff having similar properties as that of Example 4(a) is obtained.

c. A blue dyestuff having similar properties as that of Example 4(a) is also obtained by repeating the above Example, but replacing the 40.4 g of sodium salt of 1- amino-4-bromoanthraquinone-3-sulphonic acid used therein by 43.85 g of sodium salt of l-amino-4-bromo- 7-chloro-anthraquinone-Z-sulphonic acid and otherwise following the procedure given in the Example.

EXAMPLE 5 a. 40.4 g of the sodium salt of l-amino-4- bromoanthraquinone- 2-sulphonic acid, 37.2 g of 1- amino-4,5-dimethylbenzene-3-sulphonic acid-N,N-

dimethylamide (M.P. l31.5 l32.5) and 20 g of sodium bicarbonate are added to 400 ml of water. The reaction mixture is heated to and, while stirring well, 0.5 g of copper-(l) bromide are added in portions within 30 minutes. Dyestuff formation begins immediately and is completed by stirring for another 4 hours at 80 to 85. The dyestuff formed of the formula is precipitated at 40 in the form of the sodium salt by the addition of sodium chloride, filtered off and dried. It is a dark blue powder which dissolves in concentrated sulphuric acid with a greenish blue and in water with a pure blue shade. The dyestuff dyes wool and synthetic polyamide fibres from an acetic acid or sulphuric acid bath in pure blue shades which have very good fastness to light and good constancy of colour in artificial light.

b. By using instead of 37.2 g of 1-amino-4,5-

dimethylbenzene-3-sulphonic acid-N,N- dimethylamide, 32.1 g of 1-amino-4,5- dimethylbenzene-3-sulph onic acid-N-methylamide or 44.2 g of l-amino-4,5-dimethylbenzene-3-s'ulphonic acid-N-ethyl-N-isopropyl-amide and otherwise repeating the procedure as given in Example 5(a), blue dyestuffs having similar properties are obtained.

EXAMPLE 6 0 NHz S OaNa g HN- CH3 CH2-CH2 S 2N O cHrcs is precipitated at room temperature by the addition of sodium chloride, filtered off, washed with 10 percent aqueous sodium chloride solution and dried. It is a dark blue powder. The dyestuff dyes wool and synthetic polyamide fibres from an acetic acid or sulphuric acid bath in pure, level shades having good overall fastness nel is dyed at the boil for 1 hour. The dyed goods are properties. b. By using instead of the 32.4 g of l-aminothen rinsed first with warm and then with cold water 4,5-dimethylbenzene-3-sulphonic acid morpholide, and dried at 60. A very level, pure blue and light fast 35.76 g of 1-amino-4,5-diethylbenzene-3-sulphonic dyeing having very good constancy of colour in artificacid morpholide and otherwise following the procedure 5 ial light is obtained.

given in Example 6(a), a blue dyestuff having similar By using instead of acetic acid 0.1 ml of 85 percent dyeing properties is obtained. formic acid or 0.1 ml of 96 percent sulphuric acid and following the dyeing procedure as described in the EXAMPLE 7 above Example, a blue dyeing having the same propera. 53.82 g of a mixture of 1-amino-4- 10 ties is obtained. bromoanthraquinone-Z,5-or -2,8-disulphonic acid po- By using instead of IO g of wool flannel 10 g of Nytassium salt, 29.5 g of lamino-4,5-dimethylbenzene-3- Ion-6 fabric and proceeding as described above, a very sulphonic acid ethanolamide and 23 g of potassium bilevel pure and light fast blue dyeing having very good carbonate are slurried in 300 ml of water. The reaction constancy of colour in artificial light, is obtained. mixture is heated to 80 to 85 and 0.5 g of copper-(I) What is claimed is:

chloride are added within minutes. The dyestuff forl. A dyestuff of the formula mation is complete after stirring for another 3 hours at 80 to 85. The potassium salt of the dyestuff of the for- 0 NHz mula 20 S OrM+ o NH2 7..

a 1 H l is precipitated at room temperature by the addition of M represents hydrogen or an alkali metal,

potassium chloride, filtered off and dried. When isoeach of Z, and Z independently of each other reprelated, the yield of dyestuff is quantitative for all practisents lower alkyl, and

cal purposes. It is a dark blue dyestuff powder which R, and R taken together with the nitrogen atom to dissolves in concentrated sulphuric acid with a greenish which they are linked represents a morpholine or violet and in water with a blue colour. The dyestuff piperidine radical.

dyes wool from an aqueous sulphuric acid bath in level 2. A dyestuff as defined in claim 1, which is of the blue shades which have good light fastness and good formula constancy of colour in artificial light. b. A dyestuff having similar properties as that of Example 7(a) is ob- 0 NH:

tained by using instead of 29.5 g of l-amino-4,5- l

dimethylbenzene-3-sulphonic acid ethanolamide,-36 g of 1-amino-4,5-diisopropylbenzene-3-sulphonic acid ethanolamide and otherwise following the same proce- I dure as given in Example 7(a). NH

EXAMPLE 8 01120112 10 g of wool flannel are introduced into a 40 warm SO2N 0 bath containing 0.5 g of sodium sulphate, 0.4 ml of 40 CmCH, percent acetic acid and 0.2 g of dyestuff according to Example 4 in 500 ml of water. The temperature is evenly raised to the boil within 30 minutes and the flan- 

1. A DYESTUFF OF THE FORMULA
 2. A dyestuff as defined in claim 1, which is of the formula 